Water is an essential component in our life

CHAPTER 1

INTRODUCTION

1.1 Background

Water is an essential component in our life and it can be found in a very large quantity on the earth. Without water, there would be no living plant and animal. The water consumed by human originated in various forms and from various sources (Baba >et al., 2008). Lately, the popularity of bottled mineral water with consumers has increased due to the increasing contamination of water resources. According to the International Bottled Water Association (2000), natural mineral water is water that clearly comes from underground sources. It is distinguished from ordinary drinking water because it is characterized by its content of certain mineral salts and their relative proportion and the presence of trace elements of other constituents. Besides that, natural mineral water is also defined as groundwater that obtained directly for human consumption from drilled or natural sources from underground water (Malaysia’s Food Regulation, 1985).

Nowadays lifestyles have moved most of the population towards the portable and convenient bottled mineral water. With a lot of bottled mineral water brands available in the market ranging from high end names like Evian to local brands like Spritzer and Mesra, today’s consumer has lots of choices thereby making it necessary for the manufacturer of bottled mineral water to come out with unique strategies to stay up to date in this highly competitive market.

Bottled mineral water has become an importance habit in people’s everyday lives. Bottled mineral water may even be needful, in case of temporary tap water contamination. Whatever be the reason, the trend towards consuming bottled water is predicted to increase in the coming years.

Bottled water has been steadily growing over the past three decades due the dynamic sectors of the food and beverage industry. Water has endurances and sales appeal in any food service segment. It also free of sugar, calories and alcohol, and outruns juice, coffee and soda as a beverage for all day parts.

Bottled mineral water consumption in the world is increasing by an average 7% each year, inspite of the fact that bottled mineral water has a higher price. The convenience of bottled water that can be easily purchased at retail outlets and easy to get rid of is the major factor leading many to purchase bottled mineral water. These factors have led to the increasing global production of bottled water, from estimated 142 billion liters in 2002 to over 173 billion liters in 2006. Danone, Nestle, Coca-Cola and PepsiCo are the world’s top four bottled mineral water companies. Although Coca-Cola and PepsiCo are known as the big carbonated soft drinks manufacturers, they have also noted the potential in the bottled mineral water market and have been developing their brands and capabilities in this market. Although major consumers of bottled water are in Europe and North America, the most promising markets are in Asia Pacific with an annual growth rate of 15% (Frost and Sullivan, 2007).

The increase in consumption in global with a high income is mainly due to the increasing awareness of the health preserving properties of water, both in its basic, hydrating function as well as a source of precious minerals. Table 1.1 shows how the world market of bottled water in the 2008, with Mexico being the highest consumption.

Table 1.1: Per capita consumption of bottled water in leading countries (Beverage Marketing Corporation, 2008).

Country

Gallons Per Capita

2003

2008

Mexico

41.5

59.1

Italy

47.1

54.0

United Arab Emirates

25.4

39.7

Belgium

35.1

39.0

Germany

31.9

34.8

France

39.1

34.6

Spain

33.5

31.9

Lebanon

25.4

30.5

Hungary

16.2

29.2

United States

21.6

28.5

Switzerland

25.4

26.3

Austria

22.7

26.1

Thailand

20.3

26.0

Bottled mineral water is a profitable market in Malaysia. The market is set to undergo greater product differentiation with participants expected to expand into functional and to improve on packaging in order to obtain a higher share of the market. Competition is also predicted to increase with more private labels appearing in the market. Positive growth in this market has increased the interest of other manufacturers and distributors and the increasing competition is likely to support the growth in the coming years.

In Malaysia, there are differences between Natural Mineral Water (NWM) and Packaged Drinking Water (PDW). Natural mineral water is defined as groundwater obtained for human consumption from underground water resources. It contains various minerals such as Sodium, Magnesium, Potassium and Calcium. Therefore, all NMW must comply with the standards as prescribed in Schedule 26 (Regulation 360A (7)), Food Regulations 1985. Packaged drinking water shall be potable water or treated potable water other than natural mineral water that is sealed in bottles or other types of packaging and is for human consumption. The source for this PDW can be from public water supply, surface water or underground water. The simplest way to differentiate between these two types of bottled water is by the colour of the bottle cap. Multicoloured bottle caps are given for natural mineral water while white bottle caps are only for packaged drinking water

Competition from water dispensed by vending machines, the price of bottled mineral water, and growing consumer awareness of the environmental impact of bottled mineral water are found to be restraining bottled mineral water growth in Malaysia. Furthermore, the increasing of consumer’s concern for the environment, both in terms of the wastes resulting from the polyethyleneterepthalate (PET) bottles and the effect on the ecological system from wide scale water extraction, is also one of the reason for some consumers to prevent from purchasing bottled mineral water.

1.2 Statement of problem

Based on Latinopolous >et al. (1997), a serious health effect that may cause by groundwater contamination is the reason for the increasing of public concern about the quality of groundwater resource in recent years. In present, the public is getting more concerned about their health whereby they are more interested to know about the water they consume.

The most severe contamination of groundwater was recently discovered, where millions of people are at risk and consumption of these heavy metals contaminated water has caused widespread death and disease (Nickson >et al., 1998). Heavy metals are critical in this regard because of their easy uptake into the food chain and because of bioaccumulation processes (Diagomanolin >et al., 2004). It means that concentration of a chemical will increase in our bodies over time. Our body absorbed these heavy metals from the environment and they are stored at a rate that is faster than they are metabolized or excreted from the body. In traces concentration, some heavy metals like copper and zinc are essential to maintaining good health and metabolism within the human body. But if the concentration level is higher enough, even beneficial metals can be toxic and poison us.

1.3 Objectives of the study

This study tends to highlight the specific element of heavy metals present in each bottled mineral water. More specifically, the aims are:

  1. To measure the level of heavy metals in selected bottled mineral water.
  2. To compare and compile the selected analyzed water parameters with World Health Organization (WHO) and Ministry of Health (MOH) water quality guidelines.

1.4 Significant of the study

This study focus on generating data that will provide information on the concentration of the elements found in selected mineral water for public purpose. The data will help us to know whether the mineral water content present is in the amount claimed by the manufacturers or not. This is important for human consumption purpose where the public have the right to know the exact content in bottled mineral water they consume and is the bottled mineral water is safe for drinking, relatively pure from heavy metals. Humans nowadays also depend on bottled mineral water rather than tap water due to lack of contamination and it has a better taste. The concentration of these metals in the mineral water may vary depends on the location of the source and the company’s manufacturer.

1.5 Thesis outline

Overall, this thesis consist of five chapters which purposely to assist in understanding and easy to organize though writing process. The chapters in this thesis have been organized as follows:

Chapter 1 of this thesis discusses the background of the study, the statement of problem, the need for the study and lists of objectives.

Chapter 2 generally discusses on the literature review which are the theory and argumentation of the previous researcher about the topic. In this chapter, there are explanations and details about the mineral water, classification and its characteristic, groundwater, groundwater contamination, drinking water quality, trace elements, human health effect, health related guideline, bottled mineral water and lastly indication of bottled mineral water. This chapter will help us in further understanding the concept and why this topic is significant to be studied.

Chapter 3 more focuses on research methodology. In this chapter research methodology is more on the way to analyze the concentration of trace element by using inductively coupled plasma mass spectrometry (ICP-MS Perkin Elmer Series 200). It is divided into several parts which were sample collection and preparation, elemental analysis, quality assurance and control and also statistical analysis.

Chapter 4 is focusing on the result and discussion. It also include the statistical tools to analyze the precision of the data obtain in order to have a good data. It also states the results and the data interpretation between the samples.

Chapter 5 as the last chapter functions as a conclusion to the whole chapter in this thesis. It also consists of suggestion and recommendation for future study in improving the way of conducting the project. This is followed by references.

CHAPTER 2

LITERATURE REVIEW

2.1 Water distribution

Water is necessary for life due to its natural elements which play a central role and it is important in human nutrition (Naddeo >et al., 2008). Water is the fundamental constituent of animal organisms and it is the medium through which all metabolic reactions happen. Water is the medium for all biological processes and a basic and essential dietary constituent. In other words, water is essential for life and, therefore, must be available to all, adequate, safe, accessible wholesome and, above all, should not cause appreciable health hazards, as it is needed for all other types of food (Sciacca and Conti, 2009).

Malaysia which is located in the humid tropics is generally endowed with fairly abundant rainfall of 3000 mm annually (about 990 million cu/m), of which surface run-off is around 57%. However, seasonal distribution and variation, both temporally and spatially, provide some regions to be occasionally water-stressed. 60% of rain falls between November and January annually. Fast flowing of economic growth in Malaysia in the recent years, combined with periodic occurrence of lengthy drought has brought the problems of water imbalance into sharper focus, especially where development is concentrated in water stress regions. There are more people than what a river basin and groundwater can support in some regions (JPS, 2008).

From data compiled by the Department of Environment (2005), the overall trend points to a slow but steady becoming worse in the water quality of rivers around the country. River systems as a whole, with or without confining reservoirs, 97% are estimated to contribute to the raw water supply source. The increasing population growth, coupled with rapid agricultural and industrial development, the availability of small numbers of water resources to meet increasing water demand is fast becoming a pressing issue. Due to lack access to clean water resources, consumption of bottled mineral water increased (Al Fraij >et al., 1999).

2.2 Groundwater

It is estimated that more than 50% of the world’s population depends on groundwater for drinking (Fry 2005). Groundwater is the only source of drinking water for many rural and small communities (Hani 1990). Groundwater naturally results from waters that infiltrate from the land surface and percolate to the underlying strata. Groundwater must be free from organisms that are capable of causing disease and also from minerals and organic substances that could produce adverse physiological effects to make it safe for human consumption. Drinking water should be aesthetically acceptable that it should be free from apparent turbidity, colour and odour and from any objectionable taste. Drinking water should also be at a relatively sensible temperature. Water meeting these conditions is described potable, meaning that it may be consumed in any desired amount without giving any adverse effects to human’s health (Cotruvo and Vogt, 1990).

There is high interest on the quality of groundwater all over the world due to severe problems of water stress and deterioration of water quality. The quality of groundwater highly depends on the composition o, the mineralogy, recharging water and reactivity of the geological formations in aquifers, the impact of human and industrial activities and the environmental parameters that can bring effects to the geochemical mobility of certain substances (Kouras >et al., 2007).

2.2.1 Occurrence of groundwater

Groundwater forms by part of the natural water cycle and constitutes a major portion of the cycle. Voids, spaces and cracks between particles of soil, sand, gravel, rock or other materials can be a stored place for groundwater (William >et al., 1993). Groundwater is occurred in various types of geological formation and exists in permeable geologic formation called aquifers which can store and transmit water. In many areas of the world, water does not flow in and is not stored in large underground lakes or rivers. It is stored in and moves slowly through the aquifer. Groundwater resources are underutilized in most parts of Malaysia (Jasni >et al., 2006). The hydrogeology of Peninsular Malaysia could be simplified and divided into 4 major aquifers that represent in Table 2.1.

Table 2.1: Types of aquifers found in Malaysia (Minerals and Geoscience Department Malaysia, 2004)

Types

Description

Aquifers in Alluvial Deposits

Limestone/Carbonate Rock Aquifers

Aquifers in Sedimentary and Volcanic Rocks

Aquifers in Crystalline Igneous Rocks

Aquifers in the alluvial deposits occur along the coastal zones of Malaysia and are made up of Quaternary deposits consisting of gravel, sand, silt and clay. The extent, nature and composition of the alluvium vary at different localities.

This type of aquifer is made up of carbonate rocks (limestone and marble). The quality of the groundwater is generally good but has moderate to high total dissolved solids due to soluble bicarbonates.

These aquifers are represented by fractures within sandstone, quartzite, conglomerate and volcanic rocks. The water from these aquifers is generally of medium to good quality.

Fractures within crystalline rocks and associated rocks, form this type of aquifer. The quality of water is generally good to excellent with low total dissolved solids.

Based on Wilson >et al. (1983), groundwater comprises water from springs or from wells and boreholes used to catch water from the aquifers by means of pumps. Deep wells or boreholes provide usually water of excellent bacteriological quality. Groundwater is therefore often used without any treatment, except physicochemical ones to reduce hardness or eliminate off flavors and odors. The water pumped from boreholes or shallow wells, however, is easily exposed to pollution and contamination. Depending on the type of aquifer, the type of soil and its protective effect against pollution, the physicochemical characteristics of the water, and the levels of the microbial flora may be very low (Bischofberger >et al., 1990). 105-107 cfu/mL of microbial flora have been reported. In such cases, microbial and chemical contaminants may reach groundwater sources through wells, due to infiltration, leakage of solids at the surface, leaks in pipelines, effects of agricultural treatments, cross contamination between aquifers, water fluxes due to rainfalls, etc (Wilson >et al., 1983). According to Aastrup and Thunholm (2000), groundwater can be considered both as storage of metals, as the movement in the groundwater zone generally is quite slow, and as a transporting agent for metals. In natural ecosystems it is the only agent for horizontal transport within recharge areas.

2.3 Groundwater consumption in Malaysia

As surface water is readily available throughout the year, it is abstracted mainly for irrigation and domestic uses. Some pockets of the coastal region and is generally exploited by rural people to supplement their piped water supply can limiting the groundwater potential. Surface water represents 97% of the total water use, while groundwater represents 3%. About 60-65% of groundwater utilization is for domestic and municipal purposes, 5% for irrigation and 30-35% for industry (FAO, 2007).

2.4 Groundwater contamination

Since the beginning of this century, we have been living in a sophisticated chemical world (Goodarzi and Mukhopadhyay, 2000). Groundwater contamination can gives major implications to human’s health and the environment in urban areas (Dechesne >et al., 2004). The groundwater beneath polluted urban areas may be contaminated by heavy metals and trace elements and may contain a wide variety of organic compounds, all of which have a major effect on the water supply and the environment (Vidal >et al., 2000). In this chemical world, the pollutants that occur in our environment can be classified into two categories that are natural and synthetic. The natural pollutants are derived from the decay of plant substances, flow of water through rocks that contain fossil fuel and transportation as air or water borne components derived from volcanic eruptions or forest fires. Similar compounds, as those released naturally, may also be derived as a synthetic by product from anthropogenic sources. Therefore, pollutants can be derived from a number of two sources in a natural ecosystem especially in the aquatic regime. The sources of some of the pollutants are often difficult to predict and (Goodarzi and Mukhopadhyay, 2000). Goodarzi and Mukhopadhyay (2000) also claimed that the distribution of inorganic elements in the groundwater is universal. They occur as suspended particulates or dissolved as elements, ions, or complex molecules. Some of them are toxic and carcinogenic to humans and other biohabitats. Based on Zhang (1993), rapid industrial development in the last few years has added huge loads of pollutants to our groundwater aquifer. Diagomanolin >et al. (2004) also postulated that the progress of industries has led to increased emission of pollutants into ecosystems.

Contaminants can differentiate as inorganic or organic chemicals, radionuclides, and microorganisms. Mineral based and do not contain carbon are called the inorganic mineral. They may occur naturally or enter the watershed from farming or industrial discharge. Examples of inorganic contaminants are lead, nitrates, and arsenic. Organic chemicals contain carbon and access the watershed from agricultural and industrial run off. Volatile organic chemicals are persistent in the environment and have been associated with cancer and neurological and reproductive health effects. Examples include gasoline and degreasing and dry cleaning solvents. There are over 30 standards for synthetic organic chemicals, many of which are pesticides (Afzal, 2006)

Based on Leeuwen (2000), there are many sources of contamination of drinking water. Widely they can be categorized into two categories that are contaminants in ground and surface water. The sources for drinking water production and contaminants used or formed during the treatment and distribution of drinking water. Contaminants in ground and surface water will range from natural substances leaching from soil, run-off from agricultural activities, controlled discharge from sewage treatment works and industrial plants, and uncontrolled discharges or leakage from landfill sites and from chemical accidents or disasters. Contaminants that occurred naturally are predominantly formed by inorganic compounds such as arsenic and manganese, which are derived from natural mineral formations. Organic compounds, pesticides, disinfectants and disinfectant by products are usually introduced by anthropogenic activity.

Out of these pollutants, heavy metals are of major concern because of their persistent and bioaccumulative nature. Heavy metal is one of the most serious inorganic contaminants in drinking water on a worldwide region (Smedley and Kinniburgh, 2002). These heavy metals can enter into the groundwater system by weathering and erosion or anthropogenic due to industrial processing, agricultural run off and sewage disposal (Kaushik >et al., 2009). Heavy metals concentration can increase due to the industrial effluents, non-point pollution sources, as well as atmospheric precipitation (Klavins >et al., 2000). The presence of toxic pollutants in groundwater has to be avoided in order to preserve the environmental quality because it can bring about significant changes in the properties of water resources (Natale >et al., 2008).

Anthropogenic activity has often been the reason for the mobilization of natural heavy metal deposits (Vidal >et al., 2000). Heavy metal contamination in drinking water sources is known widely and has give effects to the population for many generations. Volcanic, geothermal and mining activities, in conjunction with evapoconcentration in the arid climate, are the well known causes for the increasing levels of heavy metal concentrations in groundwater (Karcher >et al., 1999). Heavy metals can be mobilized from initially inert minerals through mining activity. Acid drainage waters from mining areas can be highly enriched with toxic levels of heavy metals (Nordstrom >et al., 2000).

2.5 Mineral water

Mineral water may represent a good source of nutrition which is necessary for the needs of human body (Ekmekcioglu, 2000). Mineral water always contains various minerals and trace elements (Saleh >et al., 2001), and can be defined as water containing minerals which are natural compounds formed through geological processes or other dissolved substances that alter its taste or give it therapeutic properties which gives good healing to any disease (Warburton >et al., 1992). Human beings required minerals for nutrition, growth, sustaining body functions and well being (Baba >et al., 2008). These minerals have various effects on the human’s health (WHO, 2008). The demand for natural mineral waters is increasing due to the increasing of pollution in drinking water. The quality of drinking water is significant for health in both developing and developed countries worldwide (Cemek >et al., 2007). According to Wilson >et al. (1983), mineral water is drawn from underground sources such as a bore holes or a springs. Mineral waters are different regarding to their composition and content in minerals. Natural mineral water that comes from the groundwater is the most valuable freshwater resource on the earth (Madan >et al., 1999) and it plays an important role in drinking water supply all over the world and is often preferred for drinking water supply and it deemed to be the best water for the consumption of human (Soltan, 1999).

Natural mineral waters have long been used for medical purposes (Albu >et al., 1997). The term natural mineral water is defined as it originates in an underground water table or deposit, it differs from treated water in its original purity that is bacteriologically healthy and its content of minerals, trace minerals and other constituents, which must remain constant. Only natural mineral water has the characteristics that can benefits human health. Natural mineral water can be sparkling or still. During bottling, the carbon dioxide that causes carbonation also can be natural or added. Bottling is done at the source and treatments to make partial changes to the composition of or purify natural mineral water bacteriologically are prohibited (Cemek >et al., 2007).

Mineral water run across highly mineralised rocks. The geological sources of natural mineral water are known as aquifers, which can be from different types, and they differ greatly in terms of their depth, horizontal extent, composition, and permeability. Water filtering underground flows slowly through deep permeable rocks and sediments and diffuses into the empty interstitial space of the rocks. Water picks up minerals and other elements depending on the chemical make-up of the strata while passing through the underground strata. This is why they have higher concentrations of minerals and trace minerals than other kinds of water (Botezatu >et al., 2005).

According to Misund >et al. (1999), natural mineral water is characterized by its mineral content, trace elements or other constituents and, where appropriate, by certain effects, also by being in its original state, both conditions having been preserved intact because of the underground origin of the water which has been protected from all risk of pollution. The composition, temperature and other essential characteristics of natural mineral water must remain stable at source within the limits of natural fluctuation. In particular, they must not be affected by possible variations in the rate of flow. Mineral waters may be gaseous or non gaseous. Disinfections are not allowed in terms of treatment. The only treatment authorized is filtration or decanting and the addition or removal of carbon dioxide.

Based on Petraccia >et al. (2006), mineral waters are of underground origin, protected from contamination, and microbiologically wholesome, present a peculiar and constant chemical composition, and have favorable effects on health. To ensure it is safe, they must be bottled at source and checked containers. Mineral water does not simply mean containing minerals in fact waters that run underground and are enriched with minerals by contact with rocks cannot be considered mineral waters unless they do not possess therapeutic properties.

2.6 Classification and characteristics of mineral waters

Based on Petraccia >et al. (2006), natural mineral waters can be classified into potable waters, dietetic waters, and healing waters. Bottled dietetic waters showed that it can be used to restore salts and hydrate through experimental evidence and are useful in low sodium diets and provide the right calcium intake in particular conditions. Healing waters possess pharmacological and clinical properties related to prevention and treatment of specific pathologies. They are used in thermal establishments, under medical control, for drinking, irrigations, inhalations, and baths. The main classification parameters for mineral waters are rate of flow, temperature, freezing point, dry residues at 180oC, predominant ion composition, and predominant biological activity. The rate of flow of the spring must be stable, and ground water table must be deep, with a sufficiently large basin. Waters can be cold waters based on its temperature that is temperature at source up to 20oC and thermal waters that is temperature higher than 20oC. Based on the freezing point mineral waters are categorized into isotonic, hypotonic, and hypertonic. Freezing point is influenced by osmotic pressure and mineral concentration. Based on dry residues at 180oC that is total salts in grams after evaporation of 1 L mineral water at 180oC, waters can be divided based on their mineral contents. Table 2.2 shows the classification of mineral content in water whereas Table 2.3 shows the current Italian classification that is based on the predominant chemical elements resulting in the biological and healing effects of the mineral water.

Table 2.2: Classification of mineral content in water (Petraccia >et al., 2006)

Mineral content

Dry residue (mg/l)

Low

>50 and <500

Medium

>500 and <1500

High

>1500

Table 2.3: Current Italian classification (Petraccia >et al., 2006)

Types

Description

Bicarbonate water

bicarbonate content greater than 600mg/l

Sulfate water

sulfate content greater than 200mg/l

Chlorinated water

chloride content greater than 200mg/l

Calcium water

calcium content greater than 150mg/l

Magnesium water

magnesium content greater than 50mg/l

Fluorate water

fluoride content greater than 1mg/l

Ferrous water

bivalent iron content greater than 1mg/l

Sodium water

sodium content greater than 200mg/l

Low-salt water

sodium content greater than 20mg/l

Petraccia >et al. (2006) also reported that 9% of the waters on the market are waters with a very low mineral content. These waters have a diuretic effect and are indicated in urinary stones, facilitate uric acid clearance which is suitable for powdered milk dilution since they do not modify its formulation and also indicated in hypertension for their low sodium content. 65% of mineral waters on the market are waters with a low mineral content are. They have diuretic effects, and are strongly imply in urinary stones and gout because facilitate uric acid and ureic nitrogen clearance. 20% of the mineral waters on the market are waters with a medium mineral content. They are similar to low-mineral waters in the action, but their diuretic effect is inversely proportional to the amount of dry residues. 6% of the mineral waters on the market are waters rich in mineral salts and are defined as medicinal waters.

2.7 Drinking water quality

Water quality can give a major impact on both individuals and communities health (Cemek >et al., 2007). Water may contain substances, whether natural or through human activity, that can affect the quality and existence of life. It is important to recognize between pure water and safe water. Pure water can be defined as water that is free from all unrelated substances, whether it can be harmless to health or not and is impossible to produce. On the other hand, safe water is water that is not likely to cause undesirable or adverse effects, although it may contain certain pollutants. It should be clearly stated that drinking water should be clean and safe, and that minute quantities of contaminants present in water should meet the drinking water guideline set by the World Health Organization, to protect people’s health (Wang, 1994). Wang (1994) also stated that from the standpoint of quality, natural water resources show wide variations, especially groundwater, from low to high concentration of salt constituents, as well as other features such as physical, chemical and biological.

There is increasing concern worldwide about the quality of drinking water (Orzturk and Yilmaz, 2000). Literature reveals that the levels of some water quality constituents in drinking waters are in violation of action levels for various parameters, especially some toxic trace metals (Reimann >et al., 1999). Hudnik (1978) postulated that the increasing exploitation of mineral waters, not only for drinking waters but for medical purpose requires as complete evaluation of all the important sources as possible and not only main constituents but also trace components should be determined. Hudnik also states that the occurrence of many heavy metals can be low in mineral waters.

A reliable supply of clean drinking water is extremely important to protect the health of individuals and communities. The quantity and the quality of supply are both important. Since diseases are more easily transferred directly from person to person or via contaminated food, an adequate quantity of water is of primary importance in public health. A number of serious diseases can be spread via contaminated drinking water (Cemek >et al., 2007). Although water is important for living, poor water quality due to sewage, industrial and agricultural effluent can mean increased exposure to carcinogenic compounds, insecticides such as DDT, and heavy metals. There has been an increasing demand for natural mineral waters due to human health benefits caused the increasing contamination of tap waters and this led to more and more consumption of mineral waters and recently (Cemek >et al., 2007). Heavy metal levels in the natural waters are important indicators of water quality. The increasing concentration level of heavy metal becomes an important problem for public health. Thus, widespread and frequent monitoring surveys must be carried out.

Recent national and international regulations on water intended for human consumption explicitly exclude bottled mineral waters. World Health Organisation has guidelines for the maximum concentration of the following elements in the drinking water: As, Cd, Cr, Cu, Fe, Al, Mn, Zn, Hg and others as a guide for good drinking water quality (WHO, 1998). Guidelines or standards have to be set, giving maximum allowable concentrations for compounds in drinking water below which no significant health risk is encountered to assure consumers that drinking water is safe and can be consumed without any risk (Leeuwen 2000).

2.8 Trace elements

Our bodies required minerals are chemical elements for numerous biological and physiological processes that are needed for the maintenance of health. They are classified into two categories. Those that is required in our diet in amounts greater than 50 mg per day, called minerals, and those that are required in amounts less than 50 mg per day, which are called trace elements. Recent epidemiological studies have indicated a strong association between the occurrence of several diseases in humans and the presence of trace elements considered to be toxic such as As, Cd and Pb as well as excessive or deficient levels of essential micronutrients such as Co and Zn despite the fact that trace elements constitute only a small fraction of the total uptake food (Soupioni >et al., 2006). According to Baba >et al. (2008), trace elements are present in living organisms at very low levels but some of them are important in many different biochemical reactions that occur in the human body. Sciacca and Conti (2009) reported that in recent decades the flow from the hydrosphere to man for several heavy metals such as As, Pb and Hg has increased abundantly due to seasonal inputs by using pesticides, or to natural release from the soil into groundwater.

Based on Hsu (2005), heavy metals can be related to many anthropogenic sources and their compounds are extremely toxic and are among the most dangerous inorganic water pollutants. Many heavy metals accumulate in the aquatic food web reaching human beings through the food chain, and causing several pathologies, such as mercury, chromium and cadmium. The presence of heavy metals in groundwater is due to water exchange with contaminated rivers and lakes or to leaching from contaminated soils by rainfall infiltration. Hence, it is a major challenge for environmental engineering to remove the heavy metals from groundwater.

The presence of trace elements in groundwater is an important issue because it affects possible uses of water (Kouras >et al., 2007). Excessive levels of trace elements may occur naturally as a result of normal geological phenomena such as ore-formation or anthropogenic sources. These may be released by burning fossil fuel, mining, smelting, discharging industrial, agricultural and domestic waste, and by deliberate application of pesticides. Metals are not usually rapidly removed, nor are they readily detoxified by metabolic activity once introduced to the environment. As a result, they accumulate. Thus, their release into the ecosystem must be carefully monitored and controlled (Diagomanolin >et al., 2004).

2.8.1 Lead

Lead is a powerful neurotoxin. According to the EPA (1993), lead in drinking water can cause a variety of adverse health effects. Children should not be exposed to lead in drinking water known to be above the action level of 15 ppb. The US EPA reports that, exposure can result in delays in physical and mental development, along with deficits in attention span and learning abilities in babies and children. Hypertension may be the result of adult exposure to this element. Although the primary source of lead exposure for children and pregnant women is from lead based paint, a significant exposure can come from drinking water. Approximately 10% to 20% of background lead exposure in humans can come from drinking water, with as much as 40% to 60% for formula fed infants (US EPA, 1993).

2.8.2 Arsenic

Arsenic is a poisonous heavy metal. Particularly, arsenic contamination of groundwater is of increasing concern due to high toxicity and widespread occurrence of this element (Jain and Ali, 2000). Arsenic enters source water from erosion of natural deposits, industrial releases, agricultural runoff of arsenical pesticides, mining and smelting processes, and petroleum refining. Arsenic concentrations are higher in groundwater systems than in surface systems in the United States (US EPA, 1993). According to Afzal (2006), chronic ingestion of arsenic in contaminated drinking water is known to cause skin cancer and may increase risk for bladder, lung, kidney, liver, colon, and prostate cancers. There is also evidence that supports an association between arsenic ingestion and cardiac and cerebrovascular disease and diabetes mellitus. Arsenic, unfortunately, is present in almost all drinking water, and those that are described as chronic endemic regional hydro-arsenicosis are attributed to the use of naturally contaminated domestic water (Sciacca and Conti, 2009).

Increased concentrations of arsenic have been determined in many areas all over the world such as, in South East Asia (Bangladesh, Vietnam, West Bengal-India, Nepal, Cambodia, Mongolia, China, Thailand, Pakistan, Taiwan) in Central and South America (Argentina, Chile, Mexico) and in North America (USA and Canada) and in Australia (Kouras >et al., 2007).

2.8.3 Mercury

Mercury (Hg) contamination is a worldwide problem. The use of this metal was banned after it was proven that methylmercury (CH3Hg) is much more toxic than Hg inorganic compounds. It is formed by bacteria in anoxic areas and it caused the 1960s Minamata Bay disaster. Hg aerial emissions also have been banned, since they can be converted into CH3Hg and enter the drinking water system. This decision was taken following a federal agencies (EPA and WHO) study proving that fetuses can be seriously harmed if their mothers drink this type of water. CH3Hg also crosses the placenta to the foetus, thus producing a mutagenic and teratogenic effect, usually highlighted by a statistically significant reduction of the cerebellum weight. Exposure during pregnancy, even at low doses, can cause significant neuro-functional deficits in the newborn (WHO, 1993).

2.9 Human health effect

There are elements that are essential for growth and may have beneficial uses but eventhough these some of these trace elements are essential to human, but essential as well as non-essential elements if raise to a higher level or status can cause morphological abnormalities, reduced growth, increased mortality and mutagenic effects in humans (WHO, 1998). Based on Barnard >et al. (1997), trace metals burden in the environment can be generally reflect by the levels of trace elements in water, the amount of metals ingested through water is of extreme importance in risk assessment to human health.

There are five behaviour categories for substances in living systems. The one that considered as essential nutrients if meet deficiency will cause impairment of physiological functions that can be relieved by administration of that substance. There are many instances of both essential and nonessential compounds behaving as stimulants, causing stimulation of some metabolic processes, while others are inert or innocuous, such as tantalum, platinum, gold and silver. There are numerous compounds that serve as therapeutic agents such as the historical use of arsenic and mercury compounds against parasites and the current use of lithium in manic depression. Finally, at high concentrations most substances become toxic. They harmfully affect the activity of living organisms, perhaps irreversibly, in a manner that leads to loss of function and perhaps death. Depending on concentration and time, a single substance may act in more than one of the five ways in a single organism (Al Fraij >et al., 1999).

Misund >et al. (1999) reported violation of some drinking water permissible limits where the presence of organics and toxic elements in drinking water can lead to cancer, other human body malfunctions and chronic illnesses. There may be considerable risk to humans, especially children exposed to bottled water containing toxic elements. It is known that children may be exposed due to their behaviors, greater gastrointestinal absorption, and a lower threshold for adverse effects (Cambra and Alonso, 1995). World Health Organisation has establish maximum allowable concentration for the trace elements in drinking water as the matter of growing concern about the quality and the present of trace elements that may cause potential health hazard if they exceed certain concentrations (WHO, 1993). Many inorganic compounds, especially metal ions, play dual roles in the physiology of the organism. Some are essential for life, while most of them are toxic at elevated concentrations. Recent years have brought an increasing concern for the potential toxic effects of metal ions and other inorganic compounds which constitute part of the products and by-products of recent technologies (Al Fraij >et al., 1999).

Ions such as sodium, potassium, magnesium and calcium are essential to sustain life. Additional metals such as manganese, iron, cobalt, copper, zinc, chromium, vanadium, selenium and molybdenum are also essential for optimal growth, development and reproduction. These metals function mostly as catalysts for enzymatic activity in human bodies but become toxic, when their concentration becomes excessive. In addition to the metals essential for human metabolism, water may contain toxic metals like mercury, lead, cadmium, silver, aluminum, arsenic and barium. Epidemiological studies in recent years have indicated a strong association between the occurrence of several diseases in humans, particularly cardiovascular diseases, kidney-related disorders, neurocognitive effects and various forms of cancer and the presence of toxic trace metals (Karamanis >et al., 2007). Based on Baba >et al. (2008), up to now, there has been much debate about the health giving effects of mineral water. Apart from the obvious function of providing liquid to the body, there are no scientific studies that actually show a significant beneficial effect of mineral water on the health. While mineral water clearly contains minerals that are, in principle, beneficial for the body, the ability of the body to absorb them from mineral water is not exactly proven. But since natural water is free of any calories, sugar or artificial ingredients, it is certainly better than a sweetened, flavored soft drink. There usually being no adverse effects from drinking mineral water, we may therefore drink it just for its fresh taste.

2.10 Health related guidelines

In establishing guidelines for drinking water to protect public health, WHO (1993) applied the following definition: A guideline value represents the concentration of a constituent that does not result in any significant risk to health of the consumer over a lifetime of consumption. Although this guideline value provides a maximum level of a contaminant that may not cause any public health concern even following lifetime exposure, it does not implicate a green light for pollution of drinking water to the recommended guideline level. It must be recognized that, because water is essential to sustain life, a continuous effort should be made to maintain water quality at the highest possible level. The setting of standards might be influenced by national priorities and economic considerations and thus the conclusion on whether the health benefit of setting a specific standard justifies the costs involved is a matter of each individual country. In this way, standards can be tailored to the local situation and can be implemented and controlled in the most effective manner. Although the varying geographical situations and national needs might thus lead to different standards for drinking water quality in different countries, it must never be allowed that these considerations could endanger public health (Leeuwen, 2000). Now, WHO Guidelines for drinking water quality containing information on the health criteria for 20 selected chemicals has been published (WHO, 1998).

2.11 Bottled mineral water

Based on Gabriel (2001), over the past 25 years, bottled mineral water has climbed into a position of power in the world market. The general interest in bottled mineral water began in the late 1970s and concerns about tap water safety developed. By the 1980s, with a vigorous promotion campaign by processors of bottled water, retail sales increased and the bottled mineral water market grew faster than any other major beverage category. By the late 1990s, the bottled mineral water market was growing three times faster than soft drinks, the major beverage seller (Hunter, 2002). Through Guler (2007), the world market of bottled mineral water has grown quickly and is considered as a global billion dollar business. Bottled water consumption has been steadily growing up the last three decades in a global level and it is one of the fastest growing and the most dynamic sector of all the food and beverage industry (Ferrier, 2001).

Fresh water is insufficient, and resources are unevenly distributed throughout the world, with much of the water located far from human population (Guler, 2007). In countries with scarce water resources, consumption of bottled mineral water is a growing practice (Nsanze >et al., 1999). Growing population and the population shift from rural to urban areas have increased the consumption of bottled water world wide. According to Pip (2000), bottled mineral water has become a healthier choice than tap water for many people because they believe that bottled mineral water contains fewer contaminants, or dislike the taste of chlorinated tap water. Therefore, the annual consumption of bottled drinking water in the world is substantial. For health concern, there is increasing attention on the quality of bottled drinking water (Misund >et al., 1999). It is also stated by Saleh >et al. (2001), the dramatic increase in the consumption of bottled water worldwide has been attributed to the consumers’ concern over increasing water pollution and their objection to offensive tastes and odours such as chlorine from municipal water supplies and bacterial contamination.

Nowadays, many people living in urban areas are increasingly consuming bottled mineral water because it is seldom associated with naturalness (Saad >et al., 1998), objection to unpleasant tastes and odors from municipal water supplies (Tamagnini and Gonzalez, 1997) and because bottled mineral water is often regarded as safer as and healthier than tap water (Armas and Sutherland, 1999). Furthermore, the efficient marketing and advertising strategies followed by the bottled water producers enhanced this consumption. An evidence is the fact that especially consumers who live in developed countries buy bottled water as a healthy alternative to other beverages, to improve their diet and health. Bottled water is called the packaged water that is commercially available for human consumption (Misund >et al., 1999). Bottled mineral waters have always been regarded as a voluptuary good, something between a soft drink and a dietary or medical aid with a limited importance in human diet (Rusconi >et al., 2004). Rusconi >et al. (2004) also claimed that the increasing use of bottled mineral water makes it obvious to consider it an important element of the human diet, with special regard to children in lactation age.

According to the Misund >et al. (1999), bottled mineral water can be defined as water that is intended for human consumption and is sealed in bottles or other containers with no added ingredients except that it may contain safe and suitable anti-microbiological agents. Most bottled mineral waters are groundwater, bottled with or without some treatment process such as filtration and sterilization (Al Fraij >et al., 1999). Bottled mineral water is widely consumed because it is inexpensive, readily available, tastes better, contains fewer impurities and confers a higher social status on the consumer than tap water. Apart from the use of bottled water as drinking water, it has found wide usage in infant formula preparation and reconstituting other foods, for cleaning contact lenses, for skin care and for filling humidifiers (Warburton, 1993).

In the last years, anyway, the consumption of bottled mineral water has widely increased in all western countries. For example, in the period 1990 until 2000, mineral water consumption rose of 50% in Germany and of 130% in the USA. Italy is the main mineral water producer in the world that is 9,500 million liters have been bottled in 2000, 700 million of which have been exported. Between 1995 and 2000 the national production rose by 55% and export by 120%. Italy is also the main consumer of bottled mineral water. The national market absorbs more than 90% of the whole production (Rusconi >et al., 2004). Khan and Chohan (2009) also has postulated that according to the latest statistical report, the global consumption of bottled water reached 162 billion liters in 2005, increased by 52% from the 107 billion liters consumed 5 years earlier. This increase was quite stable with reference to population growth. However, the large consumption of bottled drinking water per person was mainly due to low level of fluoride concentration (AlDosary >et al., 2003) and apprehension about the contaminants of communal drinking water, fewer impurities, better taste, and possibly conferring higher social status (Paul >et al. 1998)

2.12 Indication of bottled mineral water

Labels on bottled mineral waters are regulated by legislative norms. Labels contain two kinds of information that are information about the producer and the production which is brand name, production lot, bottling date, bar code, the words respect the natural environment, nominal content, authorization, purchase proof, consumer service toll-free number. The label or the bottle must also show a regular hexagon or a circle with an abbreviation indicating the material of the container. The second kind of information guides the consumers in the choice of the water which best meets their requirements. The label also reports some basic rules for a correct storage of bottled mineral water that is keep in a cool, dry, clean and odorless place, away from light and heath sources. After the opening, the bottle must be closed carefully, in order to maintain the original characteristics (Petraccia >et al., 2006).

Misund >et al. (1999), reported that the regulation of contents of bottled mineral water is not stringent and the concentration printed on the labels may not be accurate. One study in Pakistan showed about 52% of bottled water was not suitable for drinking. A study (Johnson and DeBiase, 2003) was conducted in European countries to compare the actual level of different element to the concentration mentioned at the bottle.

CHAPTER 3

MATERIALS AND METHODS

3.1 Background

The evolution of directives and regulations related to public health matters is not controlled only by toxicological or epidemiological findings. Economic interest, socio-cultural characteristics, hygiene practices, public awareness and sensitivity and technological development have always been as important as scientific evidence in the establishment of regulations related to public health protection (Nsanze >et al., 1999).

As the whole human population needs drinking water for sustaining life, the provision of a safe water supply is a high priority issue for safeguarding the health and well being of humans. The production of adequate and safe drinking water is the most important factor contributing to a decrease in mortality and morbidity. To assure consumers that drinking water is safe and can be consumed without any risk, guidelines or standards have been set, giving maximum allow- able concentrations for compounds in drinking water below which no significant health risk is encountered (Leeuwen, 2000).

Therefore, standards have been developed by international, national and non-governmental organizations to define a quality of water that is safe and acceptable to consumers. Most of these standards set limits for physical parameters, chemical constituents and microorganisms that are dangerous, potentially hazardous to consumers (Guler, 2007). Table 3.1 shows the guidelines and standards for drinking water quality by World Health Organization and Ministry of Health Malaysia. Department of Environment Malaysia also revises guideline for drinking water quality from Ministry of Health Malaysia standard.

Table 3.1: WHO guideline for drinking water quality (WHO, 2008)

PARAMETER

UNIT

GUIDELINE

VALUE

Aluminium

mg/l

0.2

Arsenic

mg/l

0.01

Cadmium

mg/l

0.003

Chromium

mg/l

0.05

Copper

mg/l

2.0

Iron

mg/l

0.3

Lead

mg/l

0.01

Manganese

mg/l

0.4

Nickel

mg/l

0.07

Zinc

mg/l

3.0

Table 3.2: National guideline for drinking water quality (MOH, 2009)

PARAMETER

UNIT

GUIDELINE

VALUE

Aluminium

mg/l

0.2

Arsenic

mg/l

0.01

Cadmium

mg/l

0.003

Chromium

mg/l

0.05

Copper

mg/l

1.0

Iron

mg/l

0.3

Lead

mg/l

0.05

Manganese

mg/l

0.1

Nickel

mg/l

NA

Zinc

mg/l

3.0

Note: NA=not available

3.2 Equipment

3.2.1 Apparatus

The stability of samples, measuring, and calibration solutions depends to a high degree on the container material. The material was checked according to the specific purpose and the apparatus used in this study are stated as follows:

  1. volumetric flasks (glass), 100mL, as needed for preparation of standards and reagents.
  2. pipette, covering range of 1 to 50mL
  3. centrifuge tubes (polypropylene), 50mL, used for placing the standards solution.
  4. filter paper (glass fiber), Whatman 0.45μm
  5. vacuum/ drying apparatus

3.2.2 Instrumentation

  1. Inductively coupled plasma mass spectrometry (ICP-MS Perkin Elmer Series 200)

3.3 Reagent

For the determination of trace elements, the reagents have to be of adequate purity. The concentration of the analyte or interfering substances in the reagents and the water should be negligible compared to the lowest concentration to be determined. There are several reagents used in this study and stated as follows:

  1. deionized /milipore water
  2. nitric acid (HNO3) , 70% concentrated (SIGMA)
  3. multi-elements stock solution, 29-Multi Element Solution Standard 3 concentration 10ppm

3.4 Sample collection and preparation

Twenty brands of bottled mineral water were bought in randomly selected shops situated in different parts of Selangor which are Serdang, Sri Kembangan, Balakong, Bangi and Putrajaya. Location sources of bottled mineral water which are vary from each other is illustrated in Figure 3.1 whereas Table 3.1 shows the classification of bottled mineral water. The bottled mineral waters capacity ranged between 300 and 600ml. All brands of bottled mineral water are sold in sealed plastic bottles with the same production year.

All the apparatus were first soaked in 5% HNO3 for 24 hours and finally rinsed three times with distilled water. It was performed in clean laboratory to minimize the potential risk of contamination. Following American Public Health Association (APHA, 1998), specific analysis were done to obtain the concentration of heavy metals in each of the bottled mineral water that been tested. Volumes of 250ml of each bottled mineral waters were filtered through a glass fiber filter paper. The filtrate was acidified with concentrated HNO3 immediately to adjust the pH of water samples to pH lower than 2. All the samples were then stored at 4oC in a refrigerator prior to analysis.

Groundwater source

Table 3.3: Classification of bottled mineral water

Brand

Manufacturer (company)

Source

Container type

code

S1

C1

X1

PET

S2

C1

X1

PET

S3

C2

X2

HDPE

S4

C3

X3

HDPE

S5

C3

X3

PET

S6

C3

X3

HDPE

S7

C3

X3

PET

S8

C3

X3

HDPE

S9

C3

X3

HDPE

S10

C3

X3

HDPE

S11

C4

X4

PET

S12